Release of Nanoparticles in the Environment and Catalytic Converters Ageing.

A Three-Way Catalyst (TWC) contains a cordierite ceramic monolith coated with a layer of Al2O3, CexZr1-xO2 and platinoids mixture. Under standard operation, the platinoid concentration decreases, exposing the remaining washcoat structure. After that particle release stage, the sintering process follows where the crystalline CexZr1-xO2 solution is broken and begins to separate into ZrO2 and CeO2 phases. ZrO2 is released to the environment as micro and nanoparticles, while a small amount of CeO2 generates a new AlxCe1-xO2 composite. The main effect of Ce capture is the growth in the size of the polycrystal structure from 86.13 ± 16.58 nm to 225.35 ± 69.51 nm. Moreover, a transformation of cordierite to mullite was identified by XRD analysis. Raman spectra showed that the oxygen vacancies (Vö) concentration decreased as CexZr1-xO2 phases separation occurred. The SEM-EDS revealed the incorporation of new spurious elements and microfractures favouring the detachment of the TWC support structure. The release of ultrafine particles is a consequence of catalytic devices overusing. The emission of refractory micro to nanocrystals to the atmosphere may represent an emerging public health issue underlining the importance of implementing strict worldwide regulations on regular TWCs replacement.

Experimental and theoretical investigation on the molecular structure, spectroscopic and electric properties of 2,4-dinitrodiphenylamine, 2-nitro-4-(trifluoromethyl)aniline and 4-bromo-2-nitroaniline.

2,4-Dinitrodiphenylamine (I), 2-nitro-4-(trifluoromethyl)aniline (II) and 4-bromo-2-nitroaniline (III) have been investigated by DFT and experimental FTIR, Raman and UV-Vis spectroscopies. The gas-phase molecular geometries were consistent with similar compounds already reported in the literature. From the vibrational analysis, the main functional groups were identified and their absorption bands were assigned. Some differences were found between the calculated and the experimental UV-Vis spectra. These differences were analyzed and explained in terms of the TD-DFT/B3LYP limitations, which were mainly attributed to charge-transfer (CT) effects. These findings were in agreement with previous works, which reported that TD-DFT/B3LYP calculations diverge from experimental results when the electronic transitions involve CT. Despite this, TD-DFT/B3LYP calculations provided satisfactory results and a detailed description of the electronic transitions involved in the absorption bands of the UV-Vis spectra. In terms of the NLO properties, it was found that compound (I) is a good candidate for NLO applications and deserves further study due to its good ß values. However, the ß values for compounds (II) and (III) were negatively affected compared to those found on o-nitroaniline.